EP0344689B1 - Méthode pour mouler du polytetrafluoro-ethylène contenant une charge - Google Patents

Méthode pour mouler du polytetrafluoro-ethylène contenant une charge Download PDF

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Publication number
EP0344689B1
EP0344689B1 EP89109668A EP89109668A EP0344689B1 EP 0344689 B1 EP0344689 B1 EP 0344689B1 EP 89109668 A EP89109668 A EP 89109668A EP 89109668 A EP89109668 A EP 89109668A EP 0344689 B1 EP0344689 B1 EP 0344689B1
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EP
European Patent Office
Prior art keywords
filler
ptfe
surfactant
molding
aqueous medium
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP89109668A
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German (de)
English (en)
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EP0344689A1 (fr
Inventor
Takamichi Ishikawa
Masumi Nomura
Masuho Takeuchi
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
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Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Publication of EP0344689A1 publication Critical patent/EP0344689A1/fr
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Anticipated expiration legal-status Critical
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/04—Particle-shaped
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/25—Component parts, details or accessories; Auxiliary operations
    • B29C48/94—Lubricating
    • B29C48/95—Lubricating by adding lubricant to the moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2027/00—Use of polyvinylhalogenides or derivatives thereof as moulding material
    • B29K2027/12—Use of polyvinylhalogenides or derivatives thereof as moulding material containing fluorine
    • B29K2027/18—PTFE, i.e. polytetrafluorethene, e.g. ePTFE, i.e. expanded polytetrafluorethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2327/00—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers
    • C08J2327/02—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment
    • C08J2327/12—Characterised by the use of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08J2327/18—Homopolymers or copolymers of tetrafluoroethylene

Definitions

  • the present invention relates to a method for molding a filler-containing polytetrafluoroethylene.
  • PTFE Polytetrafluoroethylene
  • PTFE Polytetrafluoroethylene
  • PTFE has excellent heat resistance, chemical resistance, electrical properties and lubricating properties, but it has a drawback that the mechanical strength is low. Therefore, it is common to reinforce PTFE by an addition of glass fibers, graphite, bronze, carbon fibers or other inorganic powders or fibers.
  • To obtain tubes, rods or sheets of such filler-containing PTFE methods disclosed in e.g. Japanese Examined Patent Publication No. 54578/1986, Japanese Unexamined Patent Publication No.
  • a filler is mixed to a so-called fine powder, i.e. a polymer obtained by flocculating and drying a PTFE aqueous dispersion obtained by emulsion polymerization of tetrafluoroethylene (hereinafter sometimes referred to simply as TFE), to obtain a composition, and then a liquid lubricant such as naphtha or illuminating kerosine is added thereto.
  • a filler is mixed to a so-called fine powder, i.e. a polymer obtained by flocculating and drying a PTFE aqueous dispersion obtained by emulsion polymerization of tetrafluoroethylene (hereinafter sometimes referred to simply as TFE), to obtain a composition, and then a liquid lubricant such as naphtha or illuminating kerosine is added thereto.
  • TFE tetrafluoroethylene
  • the mixture is preliminarily molded and filled in a cylinder and pressed by a ram so that it is extruded through a nozzle having a shape of a tube, a rod or a sheet, whereby PTFE undergoes plastic deformation. Then, said liquid lubricant is evaporated, followed by baking to obtain a product.
  • This method is known as a paste extrusion molding method.
  • the content of the filler in such coventional filler-containing PTFE was from 0 to 30% by volume.
  • % by volume is a value obtained from the specific gravity.
  • the content of substance B in a composition comprising 20 parts by weight of substance A having a specific gravity of 2 g/cm3 and 90 parts by weight of substance B having a specific gravity of 1 g/cm3 is by volume.
  • a liquid lubricant is preliminarily incorporated in order to facilitate the plastic molding of PTFE prior to extrusion, as mentioned above.
  • the lubricant to be used for this purpose is required to be capable of readily wetting PTFE and readily removable from the extruded product, and it is further required not to leave a residue when burned and be free from coloring by baking.
  • an aliphatic or aromatic hydrocarbon or alcohol having a boiling point of from 50 to 400°C may be used as disclosed in Japanese Examined Patent Publication No. 54578/1986.
  • a liquid such as naphtha or illuminating kerosine having a boiling point of from 100 to 200°C is added in an amount of from 10 to 30%.
  • such filler not only does not undergo plastic deformation by itselt but also tends to hinder the plastic deformation of PTFE. Therefore, to obtain an extruded product of a filler-containing PTFE having practical strength and flexibility, the amount of the filler used to be reduced. Therefore, it has been difficult to obtain tubes, rods or sheets of PTFE having a high content of filler, which are dense and free from large pores and excellent in the mechanical strength.
  • the present invention has been made to solve the above-mentioned problems and provides a method for molding a filler-containing polytetrafluoroethylene, which comprises adding a surfactant-containing aqueous medium to a filler-containing polytetrafluoroethylene, followed by extrusion molding, as defined in Claim 1.
  • the polytetrafluoroethylene includes not only a homopolymer of tetrafluoroethylene but also a modified product obtained by copolymerizing other comonomer in a small amount (i.e. at a level of about 0.5 mol% or less) not to impart melt flowability.
  • a comonomer hexafluoropropylene, chlorotrifluoroethylene, perfluoro(alkyl vinyl ether), perfluoro(alkoxy vinyl ether), trifluoroethylene or perfluoroalkylethylene may be mentioned. If the molecular weight of PTFE is too low, the polymer tends to be liquid or gel-like, such being undesirable.
  • PTFE is preferably the one obtained by emulsion polymerization in view of the compatibility with the filler, or in view of the efficiency for fibrillation as described hereinafter.
  • PTFE obtained by such emulsion polymerization may further contain fine powder of PTFE obtained by other polymerization method.
  • filler may be in the form of either powder or fiber.
  • it may be a carbon material such as carbon black, carbon fiber or graphite, an oxide powder such as feldspar, silica, alumina, titanium oxide or iron oxide, an inorganic powder such as silicon nitride, carbon nitride, aluminum nitride, boron nitride, zirconium carbide, silicon carbide, tungsten carbide, nickel sulfide, zirconium sulfate, barium sulfate, kaoline, clay, glass beads or glass balloons, an inorganic fiber such as glass fiber, alumina fiber, potassium titanate fiber or silica fiber, a metal or alloy powder such as copper alloy, zinc white, molybdenum disulfide, aluminum or aluminum alloy, or an organic powder or fiber of e.g.
  • a perfluoroalkoxy resin a perfluoroethylenepropylene resin, a polychlorotrifluoroethylene resin, a polyamide resin, a polyamideimide resin, a polyetherimide resin, a polyethersulfone resin, a polyimide resin, a polyphenyleneoxide resin, a polyphenylenesulfide resin, an oxybenzoylpolyester resin, a polyetherether ketone resin or a liquid crystal polymer, may be mentioned. It is preferred to employ a filler in a powder form, particularly in a fine powder form.
  • an aqueous medium containing a surfactant is added.
  • a surfactant may be an anionic surfactant, a cationic surfactant, an amphoteric surfactant or a non-ionic surfactant.
  • the surfactant may be of a water soluble type or an oil-soluble type.
  • a water soluble type surfactant is preferably employed.
  • a fluorinated type surfactant is preferred, since it provides excellent effects in a small amount.
  • the surfactant-containing aqueous medium may contain an additive in addition to the surfactant and water.
  • an additive includes a water-soluble organic material such as an alcohol, an additive which makes a medium more viscous, or fine particles of a fluorine-containing polymer.
  • the fine particles of the fluorine-containing polymer may be not only a perfluoropolymer such as a polytetrafluoroethylene, a tetrafluoroethylene-hexafluoropropylene copolymer or a tetrafluoroethylene-perfluoro(alkyl vinyl ether) copolymer, but also an incompletely fluorinated polymer or elastomeric polymer such as an ethylene-tetrafluoroethylene copolymer, a polychlorotrifluoroethylene, a tetrafluoroethylene-propylene copolymer or a tetrafluoroethylene-vinylidene fluoride-hexafluoropropylene copolymer.
  • a perfluoropolymer such as a polytetrafluoroethylene, a tetrafluoroethylene-hexafluoropropylene copolymer or a tetrafluoroethylene-per
  • an aqueous medium containing fine particles of a fluorine-containing polymer it is preferred to employ a suspension or emulsion obtained by suspension polymerization or emulsion polymerization of a fluorine-containing monomer in a surfactant-containing aqueous medium.
  • an aqueous dispersion of polytetrafluorethylene is most preferred.
  • an aqueous dispersion containing from 1 to 90 % by weight of a polytetrafluoroethylene When the aqueous dispersion of polytetrafluoroethylene is used, the polytetrafluoroethylene remaining after molding is fibrillated, whereby a stronger molded product is obtainable.
  • a rubber latex particularly a fluorinated-type rubber latex having high affinity with PTFE, since the strength of the molded product will thereby be improved.
  • the polymer content is preferably at most 90% by weight, more preferably at most 70% by weight, particularly at most 60% by weight, in view of the stability of the aqueous medium and extrusion moldability. Further, the lower limit of the content of the fluorine-containing polymer is preferably about 5% by weight.
  • the viscosity increasing additive methyl cellulose may be mentioned. When a viscosity increasing additive is added, it is preferably at most 20% by weight, more preferably at most 10% by weight.
  • the amount of the surfactant may suitably be selected within a range of at least 0.01% by weight.
  • the amount of the surfactant is usually from 0.01 to 1.0% by weight, preferably from 0.05 to 0.5% by weight. It is usually preferred to use an organic liquid which is commonly used for extrusion molding, in combination with the above aqueous medium, whereby extrusion moldability will further be improved, and a molded product having excellent physical properties will be obtained.
  • an organic liquid solvent naphtha, illuminating kerosine, petroleum ether, isopropyl alcohol, liquid paraffin, ethylene glycol, glycerol, butylpentylphthalate or polyalkyl glycol may be mentioned. Among them, a petroleum type or aliphatic solvent is preferred.
  • the water content in the total amount of the surfactant-containing aqueous medium and the organic liquid is from 1 to 80%, more preferably from 5 to 60%, particularly from 10 to 40%.
  • the surfactant-containing aqueous medium is used usually in an amount substantially equal to the amount of an extrusion lubricant which is commonly used for extrusion molding of a filler-containing PTFE. Specifically, it is used in an amount of from 5 to 40 parts by weight, preferably from 10 to 35 parts by weight, per 100 parts by weight of the composition comprising PTFE and the filler.
  • a composition of PTFE and the filler is first prepared, and the surfactant-containing aqueous medium is added thereto prior to molding.
  • the preparation of the composition of PTFE and the filler there may be a method wherein a predetermined amount of filler is added to a dispersion of PTFE for cocoagulation, followed by drying, or a method wherein a PTFE powder and the filler are stirred and mixed.
  • the cocoagulation method is preferably employed, since the degree of fibrillation of PTFE is thereby small, and the subsequent molding operation will be easy.
  • the surfactant-containing aqueous medium is added and mixed to the composition of PTFE and the filler, such operation is preferably conducted under a condition where fibrillation of PTFE will be minimum.
  • a method it is preferred to employ a method of using a mixer which is less likely to impart mechanical shearing force (for example, an omni mixer) or a method wherein the mixing is conducted under a mild condition.
  • the composition having the surfactnat-containing aqueous medium added and mixed is preliminarily molded into blocks, followed by extrusion molding into a preform.
  • the extrusion molded product is subjected to evaporation of the aqueous medium and then baked to obtain a final product.
  • the composition may be subjected to processing such as rolling or compressing to form a sheet, followed by baking.
  • extrusion molding there is no particular restriction as to the manner of extrusion molding in the present invention.
  • a wide range of conventional techniques for extrusion molding such as, screw extrusion, ram extrusion and paste extrusion, may be employed.
  • the temperature for extrusion there is no particular restriction as to the temperature for extrusion, and it may be suitably selected within a range of not higher than the decomposition temperature of PTFE. Usually, a temperature of from 30 to 90°C is employed in view of the extrusion operation efficiency, easiness for plastic deformation of PTFE and economy.
  • RR reduction ratio
  • the molding method of the present invention is useful for molding a filler-containing PTFE.
  • the method of the present invention is effectively used for PTFE having various filler contents.
  • the filler is employed within a range of from 5 to 95% by volume, preferably from 10 to 90% by volume.
  • the difference of the present invention over the case where the conventional extrusion lubricant is employed, is remarkable particularly when the filler content is high i.e. in the molding of a highly filled PTFE.
  • the upper limit of the filler content is usually at most 95% by volume, preferably at most 90% by volume, since if the filler content is too high, molding will be difficult.
  • a processing aid a chlorine type solvent, Tricene, tradename, manufactured by Asahi Penn Chemical Company Ltd.
  • PTFE composite PTFE + filler
  • the tensile strength and the average pore diameter were measured.
  • the results are shown in Table 1 together with the pressure for paste extrusion molding and the appearance of the extruded product.
  • the tensile strength was measured by means of an Instron type universal tester in accordance with JIS K6891.
  • the average pore size was measured by means of a mercury injection type prosimeter Model 220 (manufactured by Kaluroerba Company, Italy).
  • AD-1 is a PTFE dispersion manufactured by Asahi Fluoropolymers Co., Ltd. (resin concentration: 60% by weight, nonionic surfactant: containing 3% by weight of ammonium perfluoroethyleneoxide), Softanol 30 is a nonionic surfactant, sold by Nippon Shokubai Kagaku Kogyo K.K., Metorose is hydroxypropylmethyl cellulose manufactured by Shinetsu Chemical Industries Company Limited, and Isoper M is a petroleum-type hydrocarbon manufactured by Exxon Corporation.
  • the present invention makes paste extrusion molding of a highly loaded filler-containing PTFE possible, which used to be impossible. Namely, even when a fibrous filler is employed or even when the filler is fine and used in a large amount, it is possible to obtain a uniform extrusion molding product without impairing the moldability.
  • the present invention makes it possible to prepare a excellent molded product having excellent surface smoothness and a small average pore diameter under a low extrusion pressure even when various kinds of fillers are used in various amounts as the filler for PTFE.
  • an aqueous dispersion of e.g. a fluorine resin of the present invention fine particulate solid remains in the filler-containing PTFE molded product after extrusion molding, and network effects will result when the extruded product is baked, whereby the strength is improved, and it is thereby possible to obtain an excellent product which is dense and flexible.
  • an aqueous dispersion of e.g. a fluorine resin of the present invention is used alone or used as a mixture with the aqueous liquid, it is a non-inflammable liquid, whereby it is unnecessary to provide an expensive explosion preventing installation for the molding apparatus, and the operational safety is remarkably improved.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Claims (7)

  1. Procédé pour mouler un polytétrafluoroéthyléne contenant une charge, qui comprend l'addition d'un milieu aqueux contenant un agent tensio-actif à un polytétrafluoroéthylène contenant une charge, suivie par un moulage par extrusion, dans lequel le milieu aqueux contenant un agent tensio-actif est ajouté à raison de 5 à 40 parties en poids pour 100 parties en poids du polytétra-fluoroéthylène contenant une charge, et dans lequel le polytétrafluoroéthylène contenant une charge contient de 5 à 95% en volume d'une charge.
  2. Procédé selon la revendication 1, dans lequel le milieu aqueux contenant un agent tensio-actif est un milieu aqueux contenant de 0,001 à 1,0% en poids d'un agent tensio-actif.
  3. Procédé selon la revendication 1, dans lequel le milieu aqueux contenant un agent tensio-actif est une dispersion aqueuse d'un polymère contenant du fluor.
  4. Procédé selon la revendication 1, dans lequel le milieu aqueux contenant un agent tensio-actif est une dispersion aqueuse d'un polytétrafluoroéthylène.
  5. Procédé selon la revendication 4, dans lequel la dispersion aqueuse d'un polytétrafluoroéthylène est une dispersion contenant de 1 à 90% en poids d'un polytétrafluoroéthylène.
  6. Procédé selon la revendication 1, dans lequel un liquide organique est encore ajouté avant le moulage par extrusion.
  7. Procédé selon la revendication 6, dans lequel le liquide organique est un solvant dérivé du pétrole ou un solvant aliphatique.
EP89109668A 1988-06-03 1989-05-29 Méthode pour mouler du polytetrafluoro-ethylène contenant une charge Expired - Lifetime EP0344689B1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP135639/88 1988-06-03
JP63135639A JPH07119053B2 (ja) 1988-06-03 1988-06-03 充填材入りポリテトラフルオロエチレン成形方法

Publications (2)

Publication Number Publication Date
EP0344689A1 EP0344689A1 (fr) 1989-12-06
EP0344689B1 true EP0344689B1 (fr) 1993-03-24

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US (1) US4985190A (fr)
EP (1) EP0344689B1 (fr)
JP (1) JPH07119053B2 (fr)
DE (1) DE68905525T2 (fr)

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US4153661A (en) * 1977-08-25 1979-05-08 Minnesota Mining And Manufacturing Company Method of making polytetrafluoroethylene composite sheet
JPS5730058A (en) * 1980-07-30 1982-02-18 Fujitsu Ltd Career information memory storage system
JPS59109534A (ja) * 1982-12-14 1984-06-25 Nitto Electric Ind Co Ltd ポリテトラフルオロエチレン多孔質体
US4615854A (en) * 1984-04-30 1986-10-07 Federal-Mogul Corporation Method of making a PTFE based tape suitable for impregnation into a porous metal matrix

Also Published As

Publication number Publication date
US4985190A (en) 1991-01-15
JPH07119053B2 (ja) 1995-12-20
DE68905525T2 (de) 1993-10-14
JPH01306219A (ja) 1989-12-11
EP0344689A1 (fr) 1989-12-06
DE68905525D1 (de) 1993-04-29

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